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n‐Type conjugated polymers (CPs) are crucial in the applications of organic electronics. Direct coupling of electron‐deficient C−H monomer via selective C−H activation, namely C−H/C−H oxidative direct arylation polycondensation (Oxi‐DArP), is an ideal approach toward such CPs. Herein, Oxi‐DArP is firstly adopted to synthesize a high‐performance n‐type CP using a newly developed monomer, i.e. 3,6‐di(thiazol‐5‐yl)‐diketopyrrolopyrrole (Tz‐5‐DPP). Tz‐5‐DPP based homopolymer PTz‐5‐DPP with a molecular weight of 22 kDa has been synthesized via Oxi‐DArP. After n‐doping, PTz‐5‐DPP films exhibited electric conductivity values up to 8 S cm−1 and power factors (PFs) up to 106 μW m−1 K−2. Notably, this PF value is the highest for n‐type polymer thermoelectric materials to date. The Oxi‐DArP synthesis and the excellent n‐type performance of the polymer make this work an important step toward the straightforward and sustainable preparation of high‐performance n‐type polymer semiconductors. [ABSTRACT FROM AUTHOR]